Sodium hydride → (S)-2-tert-Butoxycarbonylamino-3-(2-methyl-6-nitro-phenoxy)-propionic acid benzyl ester

HRID 1348593

Reaktionsgleichung

Reaktionsgleichung von HRID 1348593
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1[OH:11].[H-].[Na+].[C:14]([O:18][C:19]([N:21]1[C@H:25]([C:26]([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[O:27])[CH2:24]OS1(=O)=O)=[O:20])([CH3:17])([CH3:16])[CH3:15]>CN(C)C=O>[CH2:29]([O:28][C:26](=[O:27])[C@@H:25]([NH:21][C:19]([O:18][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:20])[CH2:24][O:11][C:3]1[C:4]([N+:8]([O-:10])=[O:9])=[CH:5][CH:6]=[CH:7][C:2]=1[CH3:1])[C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Komponenten

5

Edukt 3

HCID 24758Sodium hydrideHCID 831032-Methyl-6-nitrophenolHCID 866052844-Benzyl 3-(tert-butyl) (S)-1,2,3-oxathiazolidine-3,4-dicarboxylate 2,2-dioxide

Produkt 1

HCID 67076737(S)-2-tert-Butoxycarbonylamino-3-(2-methyl-6-nitro-phenoxy)-propionic acid benzyl esterAusbeute 33 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

In an inert atmosphere and under exclusion of moisture, at 0° C. a solution of 1.5 g (10 mmol) of 2-methyl-6-nitro-phenol [Ger.Offen. 3536192] in 30 ml of N,N-dimethylformamide was treated portionwise with 0.42 g (18 mmol) of sodium hydride (55% dispersion in mineral oil). After complete addition, stirring was continued for 1 hour at 0° C. Thereafter, 3.85 g (11 mmol) of (S)-2,2-dioxo-2λ6-[1,2,3]oxathiazolidine-3,4-dicarboxylic acid 4-benzyl ester 3-tert-butyl ester was added and stirring continued at 0° C. for 3 hours, then at room temperature overnight. For the working-up, the solvent was evaporated under reduced pressure, the residue treated with 100 ml of hydrochloric acid (1 N), then extracted 3 times with 150 ml of ethyl acetate. The crude product (4.0 g) was obtained as a dark brown oil which was purified by flash-chromatography on silica gel using a gradient of a 100%:0%- to 50%:50%-mixture of heptane and ethyl acetate as the eluent. There were obtained 1.4 g (33%) of the title compound as an yellow oil, [α]589=−1.45° (c=1.0% in MeOH), MS m/e (%): 431.4 (M+H+, 13).

Aufarbeitung

  1. additionAfter complete addition
  2. stirringstirring
  3. waitcontinued at 0° C. for 3 hours
  4. customat room temperature
  5. customovernight
  6. customthe solvent was evaporated under reduced pressure
  7. additionthe residue treated with 100 ml of hydrochloric acid (1 N)
  8. extractionextracted 3 times with 150 ml of ethyl acetate
  9. customThe crude product (4.0 g) was obtained as a dark brown oil which
  10. customwas purified by flash-chromatography on silica gel using a gradient of a 100%
  11. addition0%- to 50%:50%-mixture of heptane and ethyl acetate as the eluent

Quellen und Nachweise

ORD-Eintrag
ord-53a20fc3df5941e8ba2bc65252e79304
Quelldatensatz
uspto-grants-2007_05
Patentnummer
US07211573B2

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